Introduction to Ammonia Manufacture

Ammonia is generally manufactured from natural gas using the steam reforming process. Other feedstocks and
processes are used but these are not described here. There are several reaction stages and catalysts are key to the
economic operation of modern ammonia production plants. Diagram 1 illustrates the chemistry of the ammonia
process and the basic materials of the catalysts used.
The first stage is purification where impurities, mainly sulphur compounds, are removed from the gas stream.
Steam reforming is performed in two stages. In the primary stage, the endothermic reactions take place at
pressures around 30 bar and temperatures of 800C or higher. This is followed by an exothermic secondary
reformer where air is added to the partially reformed gas stream.
The carbon monoxide in the gas leaving the secondary reformer is converted to carbon dioxide in the shift reactors
and then removed by scrubbing from the gas stream. Any residual carbon oxides are then converted back to
methane by methanation before compression of the hydrogen and nitrogen to ammonia synthesis pressure.
The final reaction stage is ammonia synthesis where the hydrogen and nitrogen combine to form ammonia. This
reaction stage takes place at high pressure (100-350 bar) and is highly exothermic.
Diagram 2 shows a simplified block diagram of a typical 1000 tonne/day ammonia plant including details of
operating temperatures, catalyst volumes, KATALCOcatalyst and gas compositions.
The economics of ammonia production require careful energy management as illustrated by the flowsheet in
Diagram 3 which shows many heat exchangers are necessary to optimised heat recovery as well as to generate the
steam required for process purposes.
CHEMISTRY OF AMMONIA PROCESS
HYDRODESULPHURISER
(Sulphur Removal)
PRIMARY REFORMING
(Steam Reforming)
SECONDARY REFORMING
(Air Addition)
HIGH TEMP SHIFT
(CO Conversion)
AMMONIA SYNTHESIS
(Ammonia Formation)
METHANATOR
CO/CO Polishing
LOW TEMP SHIFT
(CO Conversion)
RSH + H RH + H S
HCI + NaAlO Al0OH + NaCL
H S + ZnO ZnS + H O
Catalyst: CoMo/NiMo
Modified Alumina
Zinc Oxide
2 2
2
2 2
CO + H O CO + H
Catalyst: Iron/Chromium/Copper
2 2 2
CO + H O CO + H
Catalyst: Copper/Zinc/Aluminium
2 2 2
N + 3H 2NH
Catalyst: Fused Promoted Magnetite
2 3 2
2
CO Removal
K CO + H O + CO 2KHCO
3 2 2 2 3
2KHCO K CO + H O + CO
3 2 3 2 2
CO + 3H CH + H O
CO +4H CH + 2H O
Catalyst: Nickel Oxide
2 2
2
4 2
4 2
Ammonia
Natural
Gas
CH + H O 3H + CO
CO + H O H + CO
Catalyst: Nickel Oxide
2
4 2
2 2
2
CH + H O 3H + CO
2H + [O + N ] 2H O + N
Catalyst: Nickel Oxide
2
4 2
2
2
2
2 2
2
Diagram 1
Simplified block diagram of typical 1000 tonne/day ammonia plant
Purification Primary Reforming Secondary
Reforming
High Temperature
CO Shift
Low Temperature
CO Shift
Methanation Ammonia
Synthesis
CO
Removal
Exit Gas Composition
N
CO
CO
CH
N + A
CO + CO
2
2
4
2
2
C
O


R
e
m
o
v
a
l
57-4
18 M
54-8
25 M
71-5
45 M
83-3
60 M
11-4
25 M
35-4/8
65 M
41-6
10 M
59-3 10M
390 C
o
790 C
o
1000 C
o
420 C
o
220 C
o
330 C
o
470 C
o
400 C
o
550 C
o
350 C
o
200 C
o
290 C
o
400 C
o
Steam
Air
Natural Gas Feed
Hydrogen
3
3
3
3 3 3 3 3 3
69.8
9.3
10.5
10.4
-
-
Volume %
56.5
12.9
7.5
0.3
22.8
-
Volume %
60.3
3.0
15.6
0.3
20.8
-
Volume %
61.4
0.3
17.8
0.2
20.3
-
Volume %
74.6
0.4
0.1
0.3
24.6
-
Volume %
74.2
-
-
0.8
25.0
5ppm
MUG
Volume %
63.4
-
-
9.5
24.9
<5ppm
NH3 - 2.5
Loop
Volume %
Ammonia
32-5 24 M
2
2
Diagram 2
indicating KATALCO catalyst types and volumes required
KATALCO KATALCO KATALCO KATALCO KATALCO KATALCO
KATALCO
KATALCO
KATALCO
Simplified flowsheet for typical ammonia plant
Natural
Gas
Steam
superheater
Air
Steam
30
bar
Steam
Steam
raising
350 C
200 C
Heat
Recovery
Steam
raising
Cooling
Cooling
Reboiler
CO
Cooling
Preheater
Heat
Recovery
Steam
Boiler
Process
Condensate
Quench
Quench
Liquid Ammonia
H
Hydrodesulphuriser Primary
Reformer
Secondary
Reformer
High
Temperature
Shift
Low
Temperature
Shift
Ammonia Synthesis CO Removal Methanator
Carbon Dioxide
Purge Gas
Cooling
400 C
o
390 C
o
2
790 C
o
550 C
o
1000 C
o
o
420 C
o
150 C
o
400 C
o
470 C
o
o
220 C
o
290 C
o
330 C
o
2
2
220 bar
Refrigeration
Condensate
Cooling
Diagram 3